Mixed esters



- stitutes therefor.

MIXED ESTERS Ernest Segcssemann, Newark, N. J., assignor to National Oil Products Company, Harrison, N. J., a. corporation of New Jersey No Drawing. Application July 6, 1940. Serial No.344,235

4 Claims. (01. zen-97.5)

selecting the fatty acids of the desired degree of The invention relates in general, to the production of valuable products from tall oiland more particularly to the manufacture of so-called mixed esters of polyhydric alcohols of the allphatic series.

"Tall oil" or talloel," which literally means pine oil" is the resinous and fatty by-product obtained in the production of paper pulpfrom resin-bearing wood by the so-called sulphate process. In this process wood is digested with an alkaline liquor containing sodium sulphate during which operation tall oil in the form of its sodium soap accumulates on the surface of the waste liquor. Tall oil, which essentially comprises a mixture of fatty and resinic' acids, is obtainable on the market in large quantities at exceedingly low prices. While some uses for tall oil have been found, the supply thereof greatly exceeds its present demand.

The general object of the present-invention is to produce new and valuable products from tall oil.

Another object of the invention is to produce low cost oils and fats which may be used as substitutes for many of the higher priced natural oilsand fats now used in various industries.

A specific object of the invention is to manufacture low cost drying oils for the paint, lacquer, varnish and other industries. 1 a

A further object of the invention is to.pro duce a low costsubstitute'for tallow and like fats.

An additional object of the invention is to produce an improved low cost substitute for sulphonated tallow and like fats.

Other objects of the invention willin part be obvious and will in part appear hereinafter.

The foregoing and other objects are accomplished according to the present invention by the production of so-called mixed esters of aliphatic polyhydric alcohols wherein at least one of the hydroxy groups is esterifled with a tall oil acid. The remaining hydroxygroups of the polyhydric .alcohol are esterifled by a saturated or unsatu- J rated higher fatty acid depending upon the type of product desired.

The present invention is particularly directed to the production of low cost drying oils or sub- In the preparation of such products at least one of the hydroxy groups of the polyhydric alcohol is esterified with a tall oil unsaturation.

Products resembling tallow and like fats may also be produced according to the invention by employing in the esterification process fatty acids of a higher degree of saturation than those used in the preparation of drying oils or substitutes therefor. These tallow substitutes are preferably produced so as to contain at. least one double bond to permit sulfonation or phosphation of the same by the usual procedures.

The foregoing mixed esters of the invention may be produced according to various specific procedures, all of which fall within the general generic process of the invention. While any suitable aliphatic polyhydric alcohol may be used inv the preparation of the esters of the invention, the use of lycerol is highly preferred. In the first esteriflcation step glycerol may be reacted with. either tall oil acids or the higher fatty acids to produce a partial ester of glycerol which is subsequently completely esterifled with acids of the type not used in the first step. Likewise, all three components may be simultaneously reacted in the properly calculated quantities to produce a glycerol ester wherein at least one hydroxy group is esterifled with a tall oil acid and at least one esterifled with .a'fatty acid. The esters of the invention may also be producedby reacting a triglyceride with glycerol to produce a partial ester and then reacting said ester with tall oil acids to produce the mixed ester, Likewise, the tall oil acids and the triglycerides may be reacted together, whereby some of the tall oil acids replace some of the fatty acids in the triglyceride molecule, thus producing a mass composed of mixed esters, free fatty acids and tall oil acids. This products possessing the features, Properties and acid and the remaining hydroxy groups are esterimay be variqi to suit the conditions at hand by the relation of elements, which are exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims.

According to the broader aspects of the inven tion, mixed esters of polyhydric alcohols are produced in which the acyl groups constitute the production ofv tallow or other fat substitutes, the

degree of unsaturation should be relatively lower.

In the preparation of the mixed esters of the invention, any suitable aliphatic polyhydric alcohol may be used including, inter alia, glycerol, glycol, glycol derivatives such as ethylene glycol, diethylene glycol, propylene glycol, etc., sorbitol, mannitol and the like. While any of the foregoing and other aliphatic polyhydric alcohols may be employed to meet the ends of the invention, it is highly preferred to use glycerol. This polyhydric alcohol is more abundant than the others, and most important of all, it yields mixed esters of greater value in that these esters possess far superior properties, particularly as far as oils and fats are concerned.

The expression tall oil acids is employed herein to connote ordinary crude or refined tall oil which essentially comprises a mixture of higher fatty acids and resin acids. It is to be understood that. the foregoing expression is also to include the higher fatty acids recovered from tall oil. In the production of the mixed esters of the invention, it is highly preferred to use tall oil which has been refined according to known processes, as by distillation of crude tall oil under reduced pressure with or without the aid of steam distillation.

In the manufacture of highly unsaturated mixed esters of the invention suitable for use as drying or semi-drying oils, the higher fatty acids employed must be highly unsaturated. It is preferred to employ the mixed fatty acids obtained by hydrolysis of natural drying oils and of semidrying oils, such as the fatty acids produced by saponification orcatalytic splitting of linseed, tung, perilla, soya-bean, menhaden, cod or like oils. Likewise, the unsaturated fatty acids of the drying oils may be used in their more purified form whenever they are commercially available,

' including, among others, linoleic, 'telfairic, elaeomargaric, linolenic, iecoric, isanic, clupanadonic,-

arachidonic, tariric and like acids. The expression drying oil fatty acids is used herein to connote the foregoing and like acids as well as those directly produced from drying or semidrying oils as aforementioned. According to the invention, the drying or semi-drying oil substitutes are produced by mixing with tall oil acids a suitable quantity of the drying oil fatty acids and an amount of .the polyhydric alcohol (prei'er ably glycerol) equivalent to or slightly in excess of that required for complete esterification of the acids, the mixture then being heated, preferably with agitation, at temperatures ranging generally from about 180 C. to just below the boiling point of the polyhydric alcohol, for about-3 to 8 hours or until esterification is substantially completed. Likewise, the polyhydric alcohol may be first partially esterified by heating at about 180 C. to 200 C. with either the tall oil acids or the drying oil fatty acids until the greater part of the acids has reacted, after which the other component perature to be varied accordingly. Moreover, the esterification steps may be carried out in an inert atmosphere as by passing a stream of a nonoxidizing gas, such as carbon dioxide, nitrogen, or the like, through the reacting mass to prevent discoloration of the product, as well as to aid in the removal of the moisture in the mass. While .the reaction will proceed without the useof catalike.

In the preparation of the more saturated esters suitable as substitutes for tallow andlike fats. the foregoing procedure is applicable, except that more highly saturated fatty acids will be used in lieu of the drying oil fatty acids. Such acids would include, inter alia, stearic, palmitic, oleic and like acids, preferably those having no points of unsaturationand in no case having more than one double bond. These more saturated mixed esters may be sulfonated according to well known methods to produce agents for use in the paper, textile, leather and other industries where sulfonated fats are employed.

. The mixed esters of the invention may also be produced by heating in a closed vessel provided with a vent for escaping water vapors and an agitator, a mixture of glycerol and a triglyceridecontaining oil of the drying type or of the saturated variety depending upon the degree of saturation required in the end product. The proportions of the glycerol and triglyceride should.

be such that mono and/or diglycerides are produced. This reaction is preferably carried out within a temperature range of about C. to 250 0., depending upon the nature of the fatty materials used and the type of partial glyceride desired. The presence of a catalyst durin the reaction is desirable, examples of which include powdered tin, zinc or aluminum, sodium or potassium alcoholates, sodium or potassium carbonates or the like. The partial glycerides thus obtained are then completely esterified by heating with an equivalent quantity of tall oil acids at a temperature ranging generally from about 180 C. to 290 C. in the presence or. not of a suitable catalyst. An inert gas may be passed through the mass during each of the reactions with advantageous results. The foregoing procedure may be slightly modified-by heating the triglyceride with the tall oil acids at about 200 C. to 300 C., thus eifecting'a re-esterification of the triglyceride and liberating a portion of the fatty acids originally combined with the triglyceride. The liberated fatty acids and remaining tall 011 acids are then 'esterified with glycerol.

. Any suitable triglyceride may be employed depending upon the type of mixed ester desired. In the production of drying or semi-drying oils, the triglyceride or oil containing the same may be selected from the drying 011 class which includes linseed oil, tung oil, perilla oil, soyabean oil, menhaden oil, cod oil, etc. When a fat or a non-drying oil substituted or the like is desired, then a more saturated oil should be used, such as cottonseed, olive,.castor and like oils, or hydrogenated fish oils, or other animal or vegetable oil, as well as polymerized oils.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to further illustrate the invention and are not to being by weight.

' of 180 to 200 C. for four hours.

aeeasoo be construed in a limiting sense, all parts given Example I 100 parts of distilled tall oil (having a resinic acid content of 32%) were heated with 26 parts of glycerol of 88% strength and 0.5 gm. of zinc oxide at 180-190 C. with rapid stirring. After five hours of heating the acid number of the mix ture dropped to below 10.0, the tall oil having been converted substantially into mono and diglycerides. At this stage 100 gms. of linseed oil fatty acids, which had been preheated to 190 Cgwere added and the heating continued in such a manner that the temperature rose gradually and reached 250 at the end of the third hour. The water evolved during the reaction was allowed to escape, the fatty acids and glycerol being returned to the reaction chamber by suitable reflux condensation. During the process or reaction a stream of carbon dioxide was allowed to pass through the reaction mass introduced by means i of an inlet tube reaching to the bottom of the vessel. The product thus obtained was a light amber-colored oil having an acid number below 5.0, generally around 3.0.

When applied to a surface, the product will dry to a flexible non-tacky film and it will dry in a sium carbonate were heated in a closed 761 provided with rapid agitation for two hours, the temperature being allowed to rise gradually and at a rate that after the second hour 210 C. was reached. The product of reaction whichAconsisted substantially of the diglyceride of hydrogenated sardine oil was cooled to 190 C. and 38 parts of tall oil having an acid value of 185 were added. This mixture was then heated at such a rate that the temperature rose gradually and after five hours it had reached 245 C. The prodnot thus obtained, consisting mainly of hydrogenated sardine oil in whichone of the fatty acid chains had been replaced with a tall oil acid chain, was a cream-colored fat of paste-dike consistency having an acid value below 5.0. It resembled. beef tallow in many respects and could be used as asubstltute for the latter in the various industries.

shorter time than the films produced by straight tall oil -glycerol esters.

Example 11 65 parts of cod oil fatty acids were mixed with 22 parts of anhydrous glycerol and 0.2 part of finely powdered tin. The mixture was then heated in an atmosphere of nitrogen at a temperature 135 parts of distilled tall 011 (having a resinic acid content 01' 38.5%) were then added slowly and at such a rate that the cooling effect of the addition did not reduce the temperature in the reaction chamber at any time to below 180 C. Heating was then continued for six additional hours, or until the acid number-oi the mixed ester had dropped to below 5.0.

| Example III 25 parts of glycerol 0! 88% strength, 70 parts oi! distilled tall oil and 130 parts oi commercial clupanadonic acid (as obtained from Armour 8:

Co., Chicago) were mixed and then heated with rapid agitation in an atmosphere of hydrogen at such. rate that after the first hour a temperature of 120 C. was reached, and that at the end of the seventh hour the temperature had risen to 260 C. The product thus obtained wasa clear oil having an acid number or less than 5.0and exhibiting excellent film-forming properties.

Example IV 100' parts of (named tall oil, 100 parts of perilla oil fatty acids, 38 parts of diethyleneglycol and 0.5 part of zinc oxide were heated with rapid agitation in an atmosphere or carbon dioxide for six hours, the temperature being regulated at such a rate that after the first hour 200 C. was reached and that at the end of the sixth hour-it had risen to 240 C. The product thus obtained was a clear, brown-colored oil having an acid number of around 10.0 and possessing good film-forming properties.

' Fitample V The following is an example for sulfonating this product: To 150 parts of the product obtained as described above, 27 parts of sulfuric acid of 98% strength "were added slowly, and at such a rate that thetemperature did not exceed 50 C. The mass was agitated for a total period of two hours while the temperature was maintained at50 C. It was then poured into a wash solution ponsisting of 300 parts of water, 15 parts of common salt" Example VI 200 parts of linseed oil were heated with 28.5

' parts of glycerol 01' 88% strength and 0.75 part of potassium carbonate for 3 hours at temperatures ranging from 200 C. to 240 C. The operation was carried out in a closed vessel provided with a rapid stirring device and with a vent to allow the escape of gases. A current of carbon dioxide was passed through the reacting masses by means of an inlet tube reaching tothe bottom of the reaction chamber. After threehours the temperature was lowered to,1'l0 C., and 200 parts parts) of l' vdrogenated sardine oil (having an iodine value or 5.0 and a'titre 0152.0 0.), 6

- ports or anhydrous-glycerol and 1 part of potasof distilled tall oil were added. and the mixture heated for 6.5 hours with agitation and under a carbon dioxide atmosphere at such a rate that the temperature rose gradually from C. to 280 C. The product thus obtained was a light, brown-colored oil having an acid value of less than 5.0. It had excellent film-forming properties, making it of value in the paint and varnish industries and other industries wherever drying oils are employed.

Example VI I 100 parts of hyd ogenated sardine oil (having an iodine value of 6.0 and a titre of 52.0 C.) were mixed with 100 parts of distilled tall oil and 2 parts of powderedtinr The mixture was then heated for-4 hours at 250 C. to 260 C and then cooled to C., whereupon 12 parts of anhydrous glycerol were added. Heating was then continued for 5 hours during which time the'temperature was allowed to rise gradually until it reached 255 q. at the end of the filth hour. The product thus obtained was a creamcolored paste having an acid value of 6 to 8.

Example VIII the original acid that forms the acyl group in v the final product. While the products of the invention have been found to be good fat and drying oil substitutes, it is evident-that they may find a wide variety of uses in many industries.

Partial mixed esters may also be produced in accordance with the invention, such, for example, as the diglycerides wherein the acyl groups constitute a tall oil acid residue and a fatty acid residue, one of the hydroxy groups remaining free.

Since certain changes in carrying out the above process and certain modifications in the products which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described and all statements of the scope of the invention, which, as. a matter of language might be said to fall therebetween; and that they are intended to be inclusive in scope and'not exclusive, in that if desired, other materials may be mal, vegetable and fish oils.

asoasoo added to my novel composition of matter herein claimed without departing from the spirit or the invention. Particularly it is to be understood that in said claims, ingredients or components recited in the singular are intended to include compatible mixtures of said ingredients wherever the sense permits.

Having described my invention, what I claim 7 substitute comprising mixed glycerol esters in which at least one of the acyl groups in each ester molecule constitutes a residue of the acids in tall oil and at least one of the acyl groups constitutes a residue of a highly unsaturated fatty acid derived from an oil selected from the group consisting of animal, vegetable and fish oils.

3. As a new composition of matter, a fat sub-' stitute comprising mixed glycerol esters in which at least one of the acyl groups in each ester molecule constitutes a residue of the acids in tall oil and at least one of the acyl groups constitutes a residue of a fatty acid containing no more than one double bond and derived from an oil selected from the group consisting of animal, vegetable and fish oils.

4. A new composition of matter, comprising a neutralized sulfated mixed glycerol ester in which at least one of the acyl groups constitutes a resldue of the acids in tall oil and at least one of acyl groups constitutes a residue of the fatty acids in an oil selected from the group consisting of ani- ERNEST SEGESSEMANN. 

